Ortho-cyanarylsulphocyanogen compounds and process of making same



Patented June 24, 1930 v UNITED STATES PATENT OFFICE RICHARD HERZ, OI FRANKFORT-ON-THE-MAIN, AND MAX SCHUBERT, OF FECHEN- HEIM, NEAR FRANKFORT-ON-THE-MAIN, GERMANY, ASSIGNORS TO GENERAL ANI- LINE WORKS, INC., 0] NEW YORK, N. Y., A CORPORATION OF DELAWARE ORTHO OYANARYLSULPHOCYANOGEN COMPOUNDS AND PROCESS OF MAKING- SAME No Drawing. Application filed March 15, 1928, Serial No. 262,032, and in Germany March 17, 1927.

ive have found that in a smooth reaction ortho-cyano-arylsulphocyanogen compoundscan be obtained by starting from orthoamlno-arylsulphocyanogen compounds of the general formula:

4 Y 1 O ary set: 2

wherein Y means that the i position is blocked, which compounds are e. g. obtainable according to the process described in an application in the name of Kaufmann and Schubert, filed March 6, 1928, Ser. No.

The diazo compounds of the ortho-aminoarylsulphocyanogen compounds are conwherein Y means that the 4-position is blocked. It is a surprising fact, that this reaction runs smoothly and leads to pure products with a very goodv yield, because these ortho-aminoaryl-sulphocyanogen compounds are rather unstable and are easily converted into the isomeric thiazole compounds by treatment in an acidic medium see Kaufmann et al., application Ser. No. 183,228, filed April 12, 1927). i

In order to further illustrate our invention, the following examples are given, the parts being by weight and all temperatures in Centigrade degrees. We wish it however to be understood that We are not limited to the particular products nor reaction conditions mentioned therein.

E wample Production of the 1-methyl-2-cyano-3-sulphocyano-fi-chlorobenzene of the formula:

O1 SON stance according to Example 3 of the aforesaid application Ser. No. 259,602, filed March 6, 1928, in the name-of Hans Kaufmann and Max Schubert, are suspended while stirringin 2,000 parts of water,mixed with 150 parts of hydrochloric acid (ai -1,15) and diazotized at about 5 with a solution of 30 parts of sodium nitrite in 500 parts of water. After about 1 hour the solution of the diazocompound is allowed to run at 5060 into 1,000 parts of a solution of cuprous cyanide, which is prepared from 84 partsof copper sulphate and 50 parts of sodium cyanide. The mass is neutralized and cooled down. The separated cyanocompound is filtered off, washed and may be directly used for the further process. It crystallizes from spirit as colorless leaflets of the melting point about 86.

Example 2 Production of the 1-cyano-2-sulphocyanogen-l-ethoxybenzene of the formula:

' H5010 SON 50 parts of 1-amino-2-sulphocyanogen-4- ethoxybenzene are dissolved in an excess of dilute hydrochloric acid and diazotized at 810 with the calculated amount of nitrite. The diazosolutionis poured at 5060 into a solution of cuprous cyanide prepared from 82 parts of copper sulphate and 58 parts of sodium cyanide with addition of 200 parts of sodium bicarbonate. After a short time the reaction mass is cooled down and the sep arated reaction product is filtered ofi, It crystallizes from spirit as colorless needles melting at 112115. It is easily soluble in organic solvents, insoluble in water and in a cold caustic soda solution.

Ewample 3 re su phocyanogen- 2 amino naphthalene I and otherwise the process is carried out in the same manner, the new 1-sulphocyanogen-2- cyano-naphthalene is obtained corresponding to the formula:

5 SON It crystallizes from spirit as colorless needles of the melting point 135136.

We claim: 1. A process which comprises diazotizing ortho-amino-aryl-sulphocyanogen compounds of the general formula:

wherein Y means that the 4-position is blocked, and treating the diazo-compounds thus formed with cuprous cyanide according to Sandmeyers reaction.

2. As new products .cyano-aryl-sulphocyanogen compounds of the general formula:

wherein Y means that the 4-position is blocked, which products are colorless crystalline substances having a definite melting point, soluble in organic solvents, insoluble in water.

3. A process which comprises diazotizing the 1-methyl-2-amino-3-sulphocyanogen- 5-ch1orobenzene of the formula:

4 Y-aryl 40 o1 soN,

and treating the diazocompound thus formed with cuprous cyanide according to Sand- 'meyers reaction.

4. As a new product the 1-methyl-2-cyano- 3-sulphocyanogen-5-chlorobenzene of the formula:

which product re resents when recrystallized from spirit color ess leaflets melting at about 86, soluble in organic solvents, insoluble in water.

In testimony whereof, we afiix our signatures.

' RICHARD HERZ. co MAX SCHUBERT. 

